Abstract:

Fluorocarbon- and urethane-(meth)acryl-containing additives and hardcoats.
The hardcoats are particularly useful as a surface layer on an optical
device.

Claims:

1. An optical display comprising:an optical substrate having a surface
layer comprising the reaction product of a mixture comprisingi) a
hydrocarbon-based hardcoat composition;ii) at least one
perfluoropolyether urethane having a perfluoropolyether moiety and at
least one terminal group comprising at least two (meth)acryl groups;iii)
at least one fluorinated compound having at least one moiety selected
from fluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least
one free-radically reactive group with a non-urethane linking group;
andiv) optionally surface modified inorganic oxide particles.

2. The optical display of claim 1 wherein the perfluoropolyether moiety of
ii) is F(CF(CF3)CF2O)aCF(CF3)-- and a ranges from 4
to 15.

3. The optical display of claim 1 wherein the linking group of iii) is
selected froma) divalent group selected from an alkylene, arylene, or
combinations thereof, optionally comprising a divalent group selected
from carbonyl, carbonyloxy, carbonylimino, sulfonamido, and combinations
thereof;b) a sulfur-containing heteroalkylene group containing a divalent
group selected from carbonyl, ester, amide, thioester or sulfonamido, and
combinations thereof;c) an oxygen-containing heteralkylene group
containing a divalent group selected from carbonyl, ester, thioester,
sulfonamido, and combinations thereof; andd) a nitrogen-containing
heteroalkylene group containing a divalent group selected from carbonyl,
amide, thioester, or sulfonamido, and combinations thereof.

4. The optical display of claim 1 wherein the free-radially reactive group
of ii), iii), and combinations thereof is a (meth)acryl group.

5. The optical display of claim 4 wherein the free-radially reactive group
of ii), iii), and combinations thereof is a (meth)acrylate group.

6. The optical display of claim 1 wherein the perfluoropolyether moiety of
iii) is F(CF(CF3)CF2O)aCF(CF3)-- and a ranges from 4
to 15.

7. The optical display of claim 1 wherein iii) has a lower molecular
weight than ii).

8. The optical display of claim 1 wherein iii) has a ratio of fluorine
atom to non-fluorine atoms that is higher than ii).

11. A fluorocarbon- and urethane-(meth)acryl-containing composition
comprising a perfluoropolyether urethane having a perfluoropolyether
moiety and a multi-(meth)acry terminal group and having the formula:
Ri--(NHC(O)XQRf)m,
--(NHC(O)OQ(A)p)n;whereinRi is the residue of a
multi-isocyanate;X is O, S or NR, wherein R is H or an alkyl group having
1 to 4 carbon;Rf is a monovalent perfluoropolyether moiety
comprising groups of the formula F(RfcO)xCdF2d--,
wherein each Rfc is independently a fluorinated alkylene group
having from 1 to 6 carbon atoms, each x is an integer greater than or
equal to 2, and wherein d is an integer from 1 to 6;each Q is
independently a connecting group having a valency of at least 2;A is a
(meth)acryl functional group --XC(O)C(R2)═CH2 wherein
R2 is an alkyl group of 1 to 4 carbon atoms or H or F;m is at least
1; n is at least 1; p is 2 to 6; m+n is 2 to 10; wherein each group
having subscripts m and n is attached to the Ri unit.

12. The composition of claim 11 with the proviso that when X is O, Q is
not methylene.

13. The composition of claim 11 wherein X is S or NR.

14. The composition of claim 11 wherein Q is an alkylene having at least
two carbon atoms.

18. The composition of claim 15 wherein Q comprises a
heteroatom-containing functional group selected from carbonyl and
sulfonyl.

19. The composition of claim 15 wherein Q is a straight chain alkylene
group comprising heteroatoms selected from O, N, S; a
heteroatom-containing functional group selected from carbonyl and
sulfonyl, and combinations thereof.

21. The composition of claim 15 wherein Q is a straight chain alkylene
group comprising heteroatoms selected from O, N, S; a
heteroatom-containing functional group selected from carbonyl and
sulfonyl, and combinations thereof.

22. The composition of claim 1 wherein Q is a nitrogen containing group.

[0002]Optical hard coats are applied to optical display surfaces to
protect them from scratching and marking Desirable product features in
optical hard coats include durability to scratches and abrasions, and
resistance to inks and stains.

[0003]Materials that have been used to date for surface protection include
fluorinated polymers, or fluoropolymers. Fluoropolymers provide
advantages over conventional hydrocarbon based materials in terms of high
chemical inertness (solvent, acid, and base resistance), dirt and stain
resistance (due to low surface energy), low moisture absorption, and
resistance to weather and solar conditions.

[0004]Fluoropolymers have also been investigated that are crosslinked to a
hydrocarbon-based hard coating formulation that improves hardness and
interfacial adhesion to a substrate. For example, it is known that
free-radically curable perfluoropolyethers provide good repellency to
inks from pens and permanent markers when added to ceramer hard coat
compositions, which comprise a plurality of colloidal inorganic oxide
particles and a free-radically curable binder precursor, such as
described in U.S. Pat. No. 6,238,798 to Kang, and assigned to 3M
Innovative Properties Company of St. Paul, Minn.

[0005]Industry would find advantage in other fluoropolymer-based hard
coatings, particularly those having improved properties.

SUMMARY OF THE INVENTION

[0006]In one aspect, the invention relates to fluorocarbon- and
urethane-(meth)acryl-containing compositions suitable for use as
additives in surface layer compositions for optical displays and other
uses.

[0007]In one embodiment, the composition comprises a perfluoropolyether
urethane having a monovalent perfluoropolyether moiety and a
multi-(meth)acryl terminal group and is described in the detailed
description below as Formula (1).

[0008]In another embodiment, the composition comprises a
perfluoropolyether-substituted urethane acrylate having a monovalent
perfluoropolyether moiety described in the detailed description below as
Formula (3A) and more preferably as Formula (3B).

[0009]In a third embodiment, the composition comprises one or more
perfluoropolyether urethanes having a monovalent perfluoropolyether
moiety and a multi-(meth)acryl group of the Formula (4) as described
further in the detailed description below.

[0010]In a fourth embodiment, the composition comprises one or more
perfluoropolyether urethanes having a monovalent perfluoropolyether
moiety and a multi-(meth)acryl group of the Formula (5) as described
below in the detailed description.

[0011]In a fifth embodiment, the composition comprises one or more
perfluoropolyether urethanes with multi-(meth)acryl groups of the Formula
(6) as described below in the detailed description.

[0012]In other embodiments, polymerizable compositions, hardcoat
composition, protective films and optical display are described having
the perfluoropolyether urethanes of Formulas 1-6, a hydrocarbon hardcoat
composition; and optionally a plurality of surface modified inorganic
nanoparticles.

[0013]In other embodiments, articles such as optical displays and
protective films are described that comprise an optical substrate having
a surface layer comprising the reaction product of a mixture comprising
i) at least one non-fluorinated crosslinking agent, and

ii) at least one perfluoropolyether urethane having a perfluoropolyether
moiety and at least one free-radically reactive group; and a hardcoat
layer comprising inorganic oxide particles disposed between the substrate
and the surface layer.

[0014]The perfluoropolyether urethane additives can improve the
compatibility of other fluorinated components such as free-radically
reactive perfluoropolyether, fluoroalkyl, or fluoroalkylene
group-containing components, such as for example
perfluorobutyl-substituted acrylate components, as well as fluoroalkyl-
or fluoroalkylene-substituted thiol or polythiol components.

[0015]In other embodiments, polymerizable coating compositions, hardcoat
surface layers, optical displays, and protective films are described
wherein the polymerizable composition comprises i) a hydrocarbon-based
hardcoat composition (e.g. a non-fluorinated crosslinking agent); ii) at
least one perfluoropolyether urethane having a perfluoropolyether moiety
and at least one free-radically reactive group; iii) and at least one
fluorinated compound having at least one moiety selected from
fluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least one
free-radically reactive group with a non-urethane linking group.

[0016]In some aspects ii) comprises at least two (meth)acryl groups such
as a terminal group having at least two (meth)acryl groups, with
(meth)acrylates groups being preferred and acrylate groups being more
preferred. Both ii) and iii) may comprise the perfluoropolyether moiety
F(CF(CF3)CF2O)aCF(CF3)-- wherein a ranges from 4 to
15. Fluorinated compound iii) may be a mono- or multi-(meth)acrylate
functional (e.g. perfluoropolyether) compound. The polymerizable
composition may have a total weight percent fluorine ranging from 0.5 to
5 wt-%. The amount of i) may comprise at least about 75 wt-% of the
mixture. Further, ii) and iii) may be present at a ratio ranging from 1:1
to 3:1. In one aspect, iii) has a ratio of fluorine atoms to non-fluorine
atoms that is higher than ii). In another aspect, iii) has a lower
molecular weight than ii).

[0017]Further, a particulate matting agent may be incorporated to impart
anti-glare properties to the optical hard coating layer. The particulate
matting agent can also prevent the reflectance decrease and uneven
coloration caused by interference of the hard coat layer with the
underlying substrate layer. In preferred embodiments, the (e.g. hardcoat)
surface layers provide any one or combination of enhanced stain and ink
repellency properties, adequate smoothness, and improved durability.

[0018]Other objects and advantages of the present invention will become
apparent upon considering the following detailed description and appended
claims, and upon reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019]FIG. 1 illustrates an article having a hard coated optical display
formed in accordance with a preferred embodiment of the present
invention.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS

[0020]For the following defined terms, these definitions shall be applied,
unless a different definition is given in the claims or elsewhere in the
specification.

[0021]The term "(meth)acryl" refers to functional groups including
acrylates, methacrylates, acrylamides, methacrylamides,
alpha-fluoroacrylates, thioacrylates and thio-methacrylates. A preferred
(meth)acryl group is acrylate.

[0022]The term "monovalent perfluoropolyether moiety" refers to a
perfluoropolyether chain having one end terminated by a perfluoroalkyl
group.

[0023]The term "ceramer" is a composition having inorganic oxide
particles, e.g. silica, of nanometer dimensions dispersed in a binder
matrix. The phrase "ceramer composition" is meant to indicate a ceramer
formulation in accordance with the present invention that has not been at
least partially cured with radiation energy, and thus is a flowing,
coatable liquid. The phrase "ceramer composite" or "coating layer" is
meant to indicate a ceramer formulation in accordance with the present
invention that has been at least partially cured with radiation energy,
so that it is a substantially non-flowing solid. Additionally, the phrase
"free-radically polymerizable" refers to the ability of monomers,
oligomers, polymers or the like to participate in crosslinking reactions
upon exposure to a suitable source of free radicals.

[0024]The term "polymer" will be understood to include polymers,
copolymers (e.g. polymers using two or more different monomers),
oligomers and combinations thereof, as well as polymers, oligomers, or
copolymers that can be formed in a miscible blend.

[0025]Unless otherwise noted, "HFPO--" refers to the end group
F(CF(CF3)CF2O)aCF(CF3)-- of the methyl ester
F(CF(CF3)CF2O)aCF(CF3)C(O)OCH3, wherein "a"
averages 2 to 15. In some embodiments, a averages between 3 and 10 or a
averages between 5 and 8. Such species generally exist as a distribution
or mixture of oligomers with a range of values for a, so that the average
value of a may be non-integer. In one embodiment a averages 6.2. This
methyl ester has an average molecular weight of 1,211 g/mol, and can be
prepared according to the method reported in U.S. Pat. No. 3,250,808
(Moore et al.), the disclosure of which is incorporated herein by
reference, with purification by fractional distillation. The recitation
of numerical ranges by endpoints includes all numbers subsumed within the
range (e.g. the range 1 to 10 includes 1, 1.5, 3.33, and 10).

[0026]As used in this specification and the appended claims, the singular
forms "a", "an", and "the" include plural referents unless the content
clearly indicates otherwise. Thus, for example, reference to a
composition containing "a compound" includes a mixture of two or more
compounds. As used in this specification and the appended claims, the
term "or" is generally employed in its sense including "and/or" unless
the content clearly dictates otherwise.

[0027]Unless otherwise indicated, all numbers expressing quantities of
ingredients, measurements of properties such as contact angle, and so
like as used in the specification and claims understood to be modified in
all instances by the term "about." Accordingly, unless indicated to the
contrary, the numerical parameters set forth in the foregoing
specification and attached claims are approximations that can vary
depending upon the desired properties sought to be obtained by those
skilled in the art utilizing the teachings of the present invention. At
the very least, and not as an attempt to limit the application of the
doctrine of equivalents to the scope of the claims, each numerical
parameter should be at least be construed in light of the number of
reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters set forth in the
broad scope of the invention are approximations, the numerical values set
forth in the specific examples are reported as accurately as possible.
Any numerical value, however, inherently contains certain errors
necessarily resulting from the standard deviations found in their
respective testing measurements.

[0028]The term "optical display", or "display panel", can refer to any
conventional optical displays, including but not limited to
multi-character multi-line displays such as liquid crystal displays
("LCDs"), plasma displays, front and rear projection displays, cathode
ray tubes ("CRTs"), and signage, as well as single-character or binary
displays such as light emitting diodes ("LEDs"), signal lamps, and
switches. The exposed surface of such display panels may be referred to
as a "lens." The invention is particularly useful for displays having a
viewing surface that is susceptible to being touched or contacted by ink
pens, markers and other marking devices, wiping cloths, paper items and
the like.

[0031]The surface energy can be characterized by various methods such as
contact angle and ink repellency, as determined by the test methods
described in the Examples. In this application, "stain repellent" refers
to a surface treatment exhibiting a static contact angle with water of at
least 70 degrees. More preferably, the contact angle is at least 80
degrees and most preferably at least 90 degrees. Alternatively, or in
addition thereto, the advancing contact angle with hexadecane is at least
50 degrees and more preferably at least 60 degrees. Low surface energy
results in anti-soiling and stain repellent properties as well as
rendering the exposed surface easy to clean.

[0032]Another indicator of low surface energy relates to the extent to
which ink from a pen or marker beads up when applied to the exposed
surface. The surface layer and articles exhibit "ink repellency" when ink
from pens and markers beads up into discrete droplets and can be easily
removed by wiping the exposed surface with tissues or paper towels, such
as tissues available from the Kimberly Clark Corporation, Roswell, Ga.
under the trade designation "SURPASS FACIAL TISSUE." Durability can be
defined in terms of results from a modified oscillating sand test (Method
ASTM F 735-94) carried out at 300 rpm for 15 minutes as described in the
Test Methods of this application. Preferably, a durable coating exhibits
an ink repellency loss value of 65 mm (75% loss) or less, more preferably
40 mm (45% loss) or less, most preferably 0 mm (no loss) of ink
repellency (IR) in this test.

[0033]Coatings appropriate for use as optical hard coatings must be
substantially free of visual defects. Visual defects that may be observed
include but are not limited to pock marks, fisheyes, mottle, lumps or
substantial waviness, or other visual indicators known to one of ordinary
skill in the art in the optics and coating fields. Thus, a "rough"
surface as described in the Experimental has one or more of these
characteristics, and may be indicative of a coating material in which one
or more components of the composition are incompatible with each other.
Conversely, a substantially smooth coating, characterized below as
"smooth" for the purpose of the present invention, presumes to have a
coating composition in which the various components, in the reacted final
state, form a coating in which the components are compatible or have been
modified to be compatible with one another and further has little, if
any, of the characteristics of a "rough" surface.

[0034]Additionally, the surface layer preferably exhibits an initial haze
of less than 2% and/or an initial transmission of at least 90%.

[0035]Referring now to FIG. 1, a perspective view of an article (here a
computer monitor 10) is illustrated as having an optical display 12
coupled within a housing 14. The optical display 12 is a substantially
transparent material having optically enhancing properties through which
a user can view text, graphics, or other displayed information. The
optical display 12 includes hard coating layer 18 applied to an optical
substrate 16. The thickness of the hardcoat layer is typically at least
0.5 microns, preferably at least 1 micron, and more preferably at least 2
microns. The thickness of the hardcoat layer is generally no greater than
25 microns. Preferably the thickness ranges from 3 microns to 5 microns.

[0036]In another embodiment (not shown), the hardcoat layer described
herein (i.e. comprising at least one fluorocarbon- and
urethane-(meth)acryl-containing additive and at least one non-fluorinated
crosslinking agent) may be provided as a surface layer having an
additional hard coat layer underlying the hardcoat surface layer. In this
embodiment, the surface layer preferably has a thickness ranging from
about 10 to 200 nanometers.

[0037]Various permanent and removable grade adhesive compositions may be
coated on the opposite side of the substrate 16 (i.e. to that of the
hardcoat 16) so the article can be easily mounted to a display surface.
Suitable adhesive compositions include (e.g. hydrogenated) block
copolymers such as those commercially available from Kraton Polymers of
Westhollow, Tex. under the trade designation "Kraton G-1657", as well as
other (e.g. similar) thermoplastic rubbers. Other exemplary adhesives
include acrylic-based, urethane-based, silicone-based, and epoxy-based
adhesives. Preferred adhesives are of sufficient optical quality and
light stability such that the adhesive does not yellow with time or upon
weather exposure so as to degrade the viewing quality of the optical
display. The adhesive can be applied using a variety of known coating
techniques such as transfer coating, knife coating, spin coating, die
coating and the like. Exemplary adhesives are described in U.S. Pat. No.
7,351,470. Several of such adhesives are commercially available from 3M
Company, St. Paul, Minn. under the trade designations 8141, 8142, and
8161.

[0038]The substrate layer 16 may consist of any of a wide variety of
non-polymeric materials, such as glass, or polymeric materials, such as
polyethylene terephthalate (PET), bisphenol A polycarbonate, cellulose
triacetate, poly(methyl methacrylate), and biaxially oriented
polypropylene which are commonly used in various optical devices. The
substrate may also comprise or consist of polyamides, polyimides,
phenolic resins, polystyrene, styrene-acrylonitrile copolymers, epoxies,
and the like. Typically the substrate will be chosen based in part on the
desired optical and mechanical properties for the intended use. Such
mechanical properties typically will include flexibility, dimensional
stability and impact resistance. The substrate thickness typically also
will depend on the intended use. For most applications, substrate
thicknesses of less than about 0.5 mm are preferred, and more preferably
about 0.02 to about 0.2 mm. Self-supporting polymeric films are
preferred. The polymeric material can be formed into a film using
conventional filmmaking techniques such as by extrusion and optional
uniaxial or biaxial orientation of the extruded film. The substrate can
be treated to improve adhesion between the substrate and the hardcoat
layer, e.g., chemical treatment, corona treatment such as air or nitrogen
corona, plasma, flame, or actinic radiation. If desired, an optional tie
layer or primer can be applied to the substrate and/or hardcoat layer to
increase the interlayer adhesion.

[0039]In the case of display panels, the substrate is light transmissive,
meaning light can be transmitted through the substrate 16 such that the
display can be viewed. Both transparent (e.g. gloss) and matte light
transmissive substrates 16 are employed in display panels 10. Matte
substrates 16 typically have lower transmission and higher haze values
than typical gloss films. The matte films exhibit this property typically
due to the presence of micron size dispersed inorganic fillers such as
silica that diffuse light. Exemplary matte films are commercially
available from U.S.A. Kimoto Tech, Cedartown, Ga. under the trade
designation "N4D2A". In case of transparent substrates, hardcoat coated
transparent substrates, as well as the display articles comprised of
transparent substrates, the haze value is preferably less than 5%, more
preferably less than 2% and even more preferably less than 1%.
Alternatively or in addition thereto, the transmission is preferably
greater than about 90%.

[0040]Various light transmissive optical films are known including but not
limited to, multilayer optical films, microstructured films such as
retroreflective sheeting and brightness enhancing films, (e.g. reflective
or absorbing) polarizing films, diffusive films, as well as (e.g.
biaxial) retarder films and compensator films such as described in U.S.
Pat. No. 7,099,083.

[0041]As described is U.S. Pat. No. 6,991,695, multilayer optical films
provide desirable transmission and/or reflection properties at least
partially by an arrangement of microlayers of differing refractive index.
The microlayers have different refractive index characteristics so that
some light is reflected at interfaces between adjacent microlayers. The
microlayers are sufficiently thin so that light reflected at a plurality
of the interfaces undergoes constructive or destructive interference in
order to give the film body the desired reflective or transmissive
properties. For optical films designed to reflect light at ultraviolet,
visible, or near-infrared wavelengths, each microlayer generally has an
optical thickness (i.e., a physical thickness multiplied by refractive
index) of less than about 1 μm. However, thicker layers can also be
included, such as skin layers at the outer surfaces of the film, or
protective boundary layers disposed within the film that separate packets
of microlayers. Multilayer optical film bodies can also comprise one or
more thick adhesive layers to bond two or more sheets of multilayer
optical film in a laminate.

[0042]Further details of suitable multilayer optical films and related
constructions can be found in U.S. Pat. No. 5,882,774 (Jonza et al.), and
PCT Publications WO 95/17303 (Ouderkirk et al.) and WO 99/39224
(Ouderkirk et al.). Polymeric multilayer optical films and film bodies
can comprise additional layers and coatings selected for their optical,
mechanical, and/or chemical properties. See U.S. Pat. No. 6,368,699
(Gilbert et al.). The polymeric films and film bodies can also comprise
inorganic layers, such as metal or metal oxide coatings or layers. The
composition of the hard coating layer 18, prior to application and curing
to the optical substrate 16, is formed from a mixture of a conventional
hydrocarbon-based, and more preferably acrylate-based, hard coat
composition and a fluorocarbon- and urethane-acrylate-containing
additive. Preferred fluorocarbon- and urethane-acrylate-containing
additive compositions are described in Formulas (1), (3A), (4), (5) and
(6) below. Methods for forming the hard coating compositions for each of
the preferred embodiments are described below in the experimental
section.

[0043]In one preferred embodiment of the present invention, the
fluorocarbon- and urethane-acrylate-containing additive is a
perfluoropolyether urethane having a monovalent perfluoropolyether moiety
and a multi-acrylate terminal group combined with a conventional
hydrocarbon-based (more preferably acrylate-based) hard coat material.
The perfluoropolyether urethane having a monovalent perfluoropolyether
moiety and a multi-acrylate terminal group is added at between about
0.01% and 10%, and more preferably between about 0.1% and 1%, of the
total solids of the hard coat composition. The additive is of the Formula
(1):

Ri--(NHC(O)XQRf)m,--(NHC(O)OQ(A)p)n (1)

wherein Ri is a residue of a multi-isocyanate; X is O, S or NR, where
R is H or lower alkyl of 1 to 4 carbon atoms; Rf is a monovalent
perfluoropolyether moiety composed of groups comprising the formula
F(RfcO)xCdF2d--, wherein each Rfc independently
represents a fluorinated alkylene group having from 1 to 6 carbon atoms,
each x independently represents an integer greater than or equal to 2,
and wherein d is an integer from 1 to 6; Q is independently a connecting
group of valency at least 2; A is a (meth)acryl functional group
--XC(O)C(R2)═CH2, where R2 is a lower alkyl of 1 to 4
carbon atoms or H or F; m is at least 1; n is at least 1; p is 2 to 6,
m+n is 2 to 10, and in which each unit referred to by the subscripts m
and n is attached to an Ri unit.

[0044]Q can be a straight or branched chain or cycle-containing connecting
group. Q can include a covalent bond, an alkylene, an arylene, an
aralkylene, an alkarylene. Q can optionally include heteroatoms such as
O, N, and S, and combinations thereof. Q can also optionally include a
heteroatom-containing functional group such as carbonyl or sulfonyl, and
combinations thereof.

[0045]By their method of synthesis, these materials are necessarily
mixtures. If the mole fraction of isocyanate groups is arbitrarily given
a value of 1.0, then the total mole fraction of m and n units used in
making materials of Formula (1) is 1.0 or greater. The mole fractions of
m:n ranges from 0.95:0.05 to 0.05:0.95. Preferably, the mole fractions of
m:n are from 0.50:0.50 to 0.05:0.95. More preferably, the mole fractions
of m:n are from 0.25:0.75 to 0.05:0.95 and most preferably, the mole
fractions of m:n are from 0.25:0.75 to 0.10:0.95.

[0046]In the instances the mole fractions of m:n total more than one, such
as 0.15:0.90, the m unit is reacted onto the isocyanate first, and a
slight excess (0.05 mole fraction) of the n units are used.

[0047]In a formulation, for instance, in which 0.15 mole fractions of m
and 0.85 mole fraction of n units are introduced, a distribution of
products is formed in which some fraction of products formed contain no m
units. There will, however, be present in this product distribution,
materials of Formula (1).

[0048]Numerous diisocyanates (di-functional isocyanates), modified
diisocyanate materials, and higher functional isocyanates may be used as
Ri in the present invention as the residue of multi-isocyanate and
still fall within the spirit of the present invention. Most preferably,
multifunctional materials based on hexamethylene diisocyanate ("HDI") are
utilized. One commercially available derivative of HDI is Desmodur®
N100, available from Bayer Polymers LLC of Pittsburgh, Pa.

[0049]Further, other diisocyanates such as toluene diisocyanate ("TDI") or
isophorone diisocyanate ("IPDI") may also be utilized as Ri in the
present invention. Non-limiting examples of aliphatic and aromatic
isocyanate materials, for example, that may be used include Desmodur®
3300, Desmodur® TPLS2294, and Desmodur® N 3600, all obtained from
Bayer Polymers LLC of Pittsburgh, Pa.

[0050]Materials used to make the additive of Formula (1) may be described
by the Formula:

[0051]HOQ(A)p, which are exemplified by, for instance, 1,3-glycerol
dimethacrylate, available from Echo Resins Inc. of Versailles, Mo.; and
pentaerythritol triacrylate, available as SR444c from Sartomer of Exton,
Pa.

[0052]Typically, the additive compositions of this preferred embodiment
are made by first reacting the polyisocyanate with the
perfluoropolyether-containing alcohol, thiol, or amine, followed by
reaction with the hydroxyl functional multiacrylate, usually in a
non-hydroxylic solvent and in the presence of a catalyst such as an
organotin compound. Alternatively, the additives of this preferred
embodiment are made by reacting the polyisocyanate with the hydroxyl
functional multiacrylate, followed by reaction with the
perfluoropolyether-containing alcohol, thiol, or amine, usually in a
non-hydroxylic solvent and in the presence of a catalyst such as an
organotin compound. In addition, the additives could be made by reacting
all three components simultaneously, usually in a non-hydroxylic solvent
and in the presence of a catalyst such as an organotin compound.

which is the reaction product of the biuret of HDI with one equivalent of
HFPO oligomer amidol
(F(CF(CF3)CF2O)aCF(CF3)C(O)NHCH2CH2OH) and
further with two equivalents of pentaerythritol triacrylate, wherein "a"
averages 2 to 15. In some embodiments, a averages between 3 and 10 or a
averages between 5 and 8.

[0054]In another embodiment, the additive composition is of the Formula
(3A):

Rf-Q--(XC(O)NHQOC(O)C(R)═CH2)f (3A)

where Rf, Q and X are the same as previously described with reference
to Formula (1) and f is 1-5.

[0055]One preferred perfluoropolyether-substituted urethane (meth)acrylate
that meets the description of Formula (3A) is described more specifically
in Formula (3B):

HFPO-Q--(XC(O)NHQOC(O)C(R)═CH2)f (3B)

[0056]Two preferred HFPO-substituted urethane acrylates that can be
utilized include
HFPO--C(O)NHC2H4OC(O)NHC2H4OC(O)C(CH3)═CH.su-
b.2 and HFPO--C(O)NHC(C2H5)(CH2OC(O)NHC2H4OC(O)C(-
CH3)═CH2)2.

[0057]In another embodiment, the additive composition is of the Formula
(4):

Ri--(NHC(O)XQRf)m,--(NHC(O)OQ(A)p)n,--(NHC(O)XQG)-
o,--(NCO)q (4)

wherein Ri is a residue of a multi-isocyanate; X, Rf and Q are
the same as previously described with reference to Formula (1). A is a
(meth)acryl functional group --XC(O)C(R2)═CH2, where
R2 is a lower alkyl of 1 to 4 carbon atoms or H or F; G is selected
from the group consisting of an alkyl, an aryl, an alkaryl and an
aralkyl. G optionally contains heteroatoms such as O, N, and S, and
combinations thereof. G also optionally has heteroatom-containing
functional groups such as carbonyl, sulfonyl, and combinations thereof.
Further, G may have a combination of heteroatoms and
heteroatom-containing functional groups. G optionally contains pendant or
terminal reactive groups. The reactive group may include (meth)acryl
groups, vinyl groups, allyl groups and --Si(OR3)3 groups, where
R3 is a lower alkyl of 1 to 4 carbon atoms. G also optionally has
fluoroalkyl or perfluoroalkyl groups. In Formula (4), m is at least 1; n
is at least 1; o is at least 1; p is 2 to 6; and q is 0 or greater.

[0058](m+n+o+q)=NNCO, the number of isocyanate groups originally
appended to Ri; and the quantity (m+n+o)/NNCO is greater than
or equal to 0.67, and in which each unit referred to by the subscripts m,
n, o, and q is attached to an Ri unit. Preferably Rfc is
--CF(CF3)CF2--.

[0059]The monoalcohol, monothiol or monoamine HXQG used in making
materials of Formula (4) may include materials such as
C4F9SO2N(CH3)CH2CH2OH,
H2NCH2CH2CH2(SiOCH3)3,
HSCH2CH2CH2Si(OCH3)3, and HEA
(hydroxyethylacrylate).

[0060]In another embodiment, the additive composition is of the Formula
(5):

wherein Ri is the residue of a multi-isocyanate; c is 1 to 50; X,
Rf, and Q are the same as previously described with reference to
Formula (1). A and G are the same as previously described with reference
to Formula 4. D is alkylene, arylene, alkarylene, fluoroalkylene,
perfluoroalkylene or aralkylene; and optionally contains heteroatoms such
as O, N, and S. D1 is alkyl, aryl, alkaryl, fluoroalkyl,
perfluoroalkyl or aralkyl; optionally containing heteroatoms such as O,
N, and S. Q1 is a connecting group defined in the same way as Q. In
Formula 5, m or z is at least 1; n or v is at least 1; y is independently
2 or greater; o, s, v, w, z and zz are 0 or greater. The sum of s, v, z
and zz is at least one. Therefore, at least one of these groups is
present.

[0061](m+n+o+[(u+1)s]+2v+w+yz+y(zz))=cNNCO the number of isocyanate
groups originally appended to Ri. The quantity
(m+n+o+([(u+1)s]+2v+yz+y(zz))/(cNNCO) is greater than or equal to
least 0.75. In Formula 5, p is 2 to 6; t is 1 to 6; and u is
independently 1 to 3; in which each unit referred to by the subscripts m,
n, o, s, v, w, z and zz is attached to an Ri unit. Preferably
Rfc is --CF(CF3)CF2--.

[0062]In this embodiment, when added to the conventional hydrocarbon-based
hard coating material, care must be taken in choosing the ratios and
amounts of reactive components to avoid highly crosslinked urethane
polymer gels. For instance, if a trifunctional isocyanate is to be used
with a multifunctional alcohol, the amount of multifunctional alcohol
should be limited to avoid forming a crosslinked network. For higher
numbers of c for (Ri)c groups, it is preferred that the
formulation be based primarily on diols and diisocyanates.

[0063]The materials used to make the additive of Formula (5) include those
of the formula Rf(Q)(XH)y, which is exemplified by
HFPO--C(O)NHCH2CH2CH2N(CH2CH2OH)2.

[0064]The materials used to make the additive of Formula (5) include those
of the formula: HXQDQXH, which is exemplified by hydrocarbon polyols such
as HO(CH2)10OH and fluorochemical diols such as
HOCH2(CF2)4CH2OH.

[0065]The materials used to make the additive of Formula (5) may include
those of the formula D(QXH)y)zz, which is exemplified by
fluorochemical diols C4F9SO2N(CH2CH2OH)2.

[0066]The materials used to make the additive of Formula (5) may also
include those of the formula HOQ(A)tQ1Q(A)tOH, which is
exemplified by hydantoin hexaacrylate (HHA), prepared as described in
Example 1 of U.S. Pat. No. 4,262,072 to Wendling et al, and
CH2═C(CH3)C(O)OCH2CH(OH)CH2O(CH2)4OCH.s-
ub.2CH(OH)CH2OC(O)C(CH3)═CH2.

[0067]In still another embodiment the additive composition is of the
Formula (6):

wherein Ri is the residue of a multi-isocyanate; c is 1 to 50; X,
Rf, Q, Q1, A, G, D, and D1 are the same as previously
described with reference to Formula (5). Rf2 is a multi-valent
fluoropolyether moiety, Rf2 is composed of groups comprising the
formula Y(Rfc1O)xCd1 F2d1)b, wherein each
Rfc1 independently represents a fluorinated alkylene group having
from 1 to 6 carbon atoms: each x independently represents an integer
greater than or equal to 2, and d1 is an integer from 0 to 6. Y
represents a polyvalent organic group or covalent bond having a valence
of b, and b represents an integer greater than or equal to 2. In Formula
(5), r is at least 1; n or v is at least 1; y is independently 2 or
greater. Further, m, o, s, v, w and zz are 0 or greater.

[0068](m+n+o+[(u+1)r]+[(u+1)s]+2v+w+y(zz))=cNNCO the number of
isocyanate groups originally appended to Ri. The quantity
(m+n+o+[(u+1)r]+[(u+1)s]+2v+y(zz))/(cNNCO) is greater than or equal
to least 0.75.

[0069]In Formula (5), p is 2 to 6; t is 1 to 6; u is independently 1 to 3;
in which each unit referred to by the subscripts m, n, o, r, s, v, w, and
zz is attached to an Ri unit. Rfc1 is preferably independently
selected from --CF(CF3)CF2--, --CF2CF2CF2--, and
(--CH2C(R)(CH2OCH2CdF2d+1)CH2--)aa
where aa is 2 or greater and d and R are defined above.

[0070]The materials used to make the additive of Formula (9) may also
include those of the formula HXQRf2QXH, which is exemplified by
(H(OCH2C(CH3)(CH2OCH2CF3)CH2)aaOH)
(Fox-Diol, having a MW about 1342 and available from Omnova Solutions
Inc. of Akron, Ohio).

[0071]For each of the formulas (I.e. Formulas 1-6) described herein, when
X is O, Q is typically not methylene and thus contains two or more carbon
atoms. In some embodiments, X is S or NR. In some embodiments, Q is an
alkylene having at least two carbon atoms. In other embodiments, Q is a
straight chain, branched chain, or cycle-containing connecting group
selected from arylene, aralkylene, and alkarylene. In yet other
embodiments, Q is a straight chain, branched chain, or cycle-containing
connecting group containing a heteroatom such as O, N, and S and/or a
heteroatom containing functional groups such as carbonyl and sulfonyl. In
other embodiments, Q is a branched or cycle-containing alkylene group
that optionally contains heteroatoms selected from O, N, S and/or a
heteroatom-containing functional group such as carbonyl and sulfonyl. In
some embodiments Q contains a nitrogen containing group such as amide.

[0072]The fluorocarbon- and urethane-(meth)acryl additive(s) described
herein can be employed as the sole perfluoropolyether containing additive
in a hardcoat composition. Alternatively, however, the additive(s)
described herein may be employed in combination with various other
fluorinated compounds having at least one moiety selected from
fluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least one
free-radically reactive group with a non-urethane linking group. In these
embodiments, the fluorocarbon- and urethane-(meth) acryl compositions(s)
can be added to the curable mixture such that the weight ratio of the
fluorocarbon urethane additive to non-urethane fluorinated material(s) is
1:1, preferably 2:1 and most preferably 3:1. Within these preferred
ratios it is possible to have the total weight percent fluorine(F) of the
curable mixture comprise from 0.5-25 wt % F, preferably 0.5 to 10 wt % F
and most preferably 0.5 to 5 wt % F.

[0073]The perfluoropolyether moiety of the urethane is preferably a HFPO
moiety, as previously described. Further, the fluorinated moiety of the
second (non-urethane) compound is also preferably a HFPO moiety.

[0074]In some embodiments, the non-urethane linking group is a divalent
group selected from an alkylene, arylene, or combinations thereof and
optionally containing a divalent group selected from carbonyl, ester,
amide, thioester or sulfonamido, and combinations thereof. In other
embodiments, the linking group is a sulfur-containing heteroalkylene
group containing a divalent group selected from carbonyl, ester, amide,
thioester or sulfonamido, and combinations thereof. In other embodiments,
the linking group is an oxygen-containing heteroalkylene group containing
a divalent group selected from carbonyl, ester, thioester, sulfonamido,
and combinations thereof. In yet other embodiments, the linking group is
a nitrogen-containing heteroalkylene group containing a divalent group
selected from carbonyl, amide, thioester, or sulfonamido, and
combinations thereof.

[0075]A variety of (per)fluoropolyether (meth)acryl compounds may be
employed in the (e.g. hardcoat) coating compositions in combination with
the fluorocarbon- and urethane-(meth) acryl compositions.
Perfluoropolyether (meth)acryl compounds can be represented by the
following Formula (7):

(Rf)--[(W)--(RA)]W (Formula 7)

wherein Rf is a (per)fluoropolyether group; W is a linking group; and
RA is a is a free-radically reactive such as (meth)acryl, --SH,
allyl, or vinyl, and is preferably a (meth)acryl group or
--COCF═CH2; and w is 1 or 2.

[0076]The perfluoropolyether group Rf can be linear, branched,
cyclic, or combinations thereof and can be saturated or unsaturated. The
perfluoropolyether has at least two catenated oxygen heteroatoms.
Exemplary perfluoropolyethers include, but are not limited to, those that
have perfluorinated repeating units selected from the group of
--(CpF2p)--, --(CpF2pO)--, --(CF(Z))--, --(CF(Z)O)--,
--(CF(Z)CpF2pO)--, --(CpF2pCF(Z)O)--,
--(CF2CF(Z)O)--, or combinations thereof. In these repeating units,
p is typically an integer of 1 to 10. In some embodiments, p is an
integer of 1 to 8, 1 to 6, 1 to 4, or 1 to 3. The group Z is a
perfluoroalkyl group, perfluoroether group, perfluoropolyether, or a
perfluoroalkoxy group, all of which can be linear, branched, or cyclic.
The Z group typically has no more than 12 carbon atoms, no more than 10
carbon atoms, or no more than 9 carbon atoms, no more than 4 carbon
atoms, no more than 3 carbon atoms, no more than 2 carbon atoms, or no
more than 1 carbon atom. In some embodiments, the Z group can have no
more than 4, no more than 3, no more than 2, no more than 1, or no oxygen
atoms. In these perfluoropolyether structures, the different repeat units
can be distributed randomly along the chain.

[0077]Rf can be monovalent or divalent. In some compounds where
Rf is monovalent, the terminal groups can be (CpF2p+1)--,
(CpF2p+1O)--, (CpF2pO)--, or
(X'CpF2p+1)--where X' is hydrogen, chlorine, or bromine and p
is an integer of 1 to 10. In some embodiments of monovalent Rf
groups, the terminal group is perfluorinated and p is an integer of 1 to
10, 1 to 8, 1 to 6, 1 to 4, or 1 to 3. Exemplary monovalent Rf
groups include CF3O(C2F4O)nCF2--,
C3F7O(CF2CF2CF2O)nCF2CF2--, and
C3F7O(CF(CF3)CF2O)nCF(CF3)-- wherein n has
an average value of 0 to 50, 1 to 50, 3 to 30, 3 to 15, or 3 to 10.

[0078]Suitable structures for divalent Rf groups include, but are not
limited to,
--CF2O(CF2O)q(CF2F4O)nCF2--,
--(CF2)3O(C4F8O)n(CF2)3--,
--CF2O(C1-2F4O)nCF2--,
--CF2CF2O(CF2CF2CF2O)CF2CF2--, and
--CF(CF3)(OCF2CF(CF3))sOCtF2tO(CF(CF3)-
CF2O)CF(CF3)--, wherein q has an average value of 0 to 50, 1 to
50, 3 to 30, 3 to 15, or 3 to 10; n has an average value of 0 to 50, 3 to
30, 3 to 15, or 3 to 10; s has an average value of 0 to 50, 1 to 50, 3 to
30, 3 to 15, or 3 to 10; the sum (n+s) has an average value of 0 to 50 or
4 to 40; the sum (q+n) is greater than 0; and t is an integer of 2 to 6.

[0079]As synthesized, compounds according to Formula (7) typically include
a mixture of Rf groups. The average structure is the structure
averaged over the mixture components. The values of q, n, and s in these
average structures can vary, as long as the compound has a number average
molecular weight of at least about 400. Compounds of Formula (7) often
have a molecular weight (number average) of 400 to 5000, 800 to 4000, or
1000 to 3000.

[0080]The linking group W between the perfluoropolyether segment and
(meth)acryl or --COCF═CH2 end group includes a divalent group
selected from an alkylene, arylene, heteroalkylene, or combinations
thereof and an optional divalent group selected from carbonyl, ester,
amide, sulfonamido, or combinations thereof. W can be unsubstituted or
substituted with an alkyl, aryl, halo, or combinations thereof. The W
group typically has no more than 30 carbon atoms. In some compounds, the
W group has no more than 20 carbon atoms, no more than 10 carbon atoms,
no more than 6 carbon atoms, or no more than 4 carbon atoms. For example,
W can be an alkylene, an alkylene substituted with an aryl group, or an
alkylene in combination with an arylene or an alkyl ether or alkyl
thioether linking group.

[0081]The perfluoropolyether acrylate compounds (e.g. of Formula 7) can be
synthesized by known techniques such as described in U.S. Pat. Nos.
3,553,179 and 3,544,537 as well as U.S. Pat. No. 7,094,829,
"Fluorochemical Composition Comprising a Fluorinated polymer and
Treatment of a Fibrous Substrate Therewith".

[0082]Suitable (non-urethane) perfluoropolyether fluorocarbon (meth)acryl
compounds include for example
HFPO--C(O)NHCH2CH2OC(O)CH═CH2,
HFPO--C(O)NHCH2CH2OCH2CH2OCH2CH2OC(O)CH.dbd-
.CH2HFPO--C(O)NH--(CH2)6OC(O)CH═CH2 and various
other (per)fluoropolyether acryl compounds such as described in U.S. Pat.
No. 7,342,080 and US Publication No. 2005/0249940; incorporated by
reference.

[0083]The (non-urethane) fluoropolyether poly(meth)acryl compound may also
have the formula (HFPO--)nQ3(X)m wherein n is 1 to 3;

Q3 is a straight chain, branched chain or cycle-containing connecting
group having a valency of at least 2 and is selected from the group
consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an
alkarylene; optionally containing heteroatoms O, N, and S, a
heteroatom-containing functional group such as carbonyl or sulfonyl, and
combinations thereof; and X is a free-radically reactive group such as
(meth)acryl, --SH, allyl, or vinyl, and is preferably a (meth)acryl
functional group AC(O)C(R)═CH2, where A is O, S or NR1, R
is a lower alkyl of 1 to 4 carbon atoms or H or F, R1 is H or lower
alkyl of 1 to 4 carbon atoms, and m is 2-10.

[0084]One compound is
B--O(CH2CH(OB)CH2O)nCH2CH(OB)CH2O--B wherein n ranges
from 0 to 20, B is independently H, --C(O)CH═CH2, or
--C(O)--HFPO, and in which at least one B is --C(O)--HFPO and at least
two B are --C(O)CH═CH2.

[0085]The (non-urethane) fluoropolyether poly(meth)acryl compound may be
the reaction product of

[0087]R6 is independently H or
CH2═C(CH3)C(O)--OCH2CH(OH)CH2--,and n ranges from
an average about 2 to 3

[0088]The (e.g. non-urethane) fluoropolyether poly(meth)acryl compound may
include any one or combination of the following compounds

HFPO--C(O)NHC(CH2OC(O)CH═CH2)3;

HFPO--C(O)N(CH2CH2OC(O)CH═CH2)2;

HFPO--C(O)NHCH2CH2N(C(O)CH═CH2)CH2OC(O)CH═CH.s-
ub.2;

HFPO--C(O)NHC(CH2OC(O)CH═CH2)2H;

HFPO--C(O)NHC(CH2OC(O)CH═CH2)2CH3;

HFPO--C(O)NHC(CH2OC(O)CH═CH2)2CH2CH3;

HFPO--C(O)NHCH2CH(OC(O)CH═CH2)CH2OC(O)CH═CH2;

HFPO--C(O)NHCH2CH2CH2N(CH2CH2OC(O)CH═CH2-
)2;

HFPO--C(O)OCH2C(CH2OC(O)CH═CH2)3;

HFPO--C(O)NH(CH2CH2N(C(O)CH═CH2))4CH2CH2-
NC(O)--HFPO;

[0089]CH2═CHC(O)OCH2CH(OC(O)HFPO)CH2OCH2CH(OH)CH.s-
ub.2OCH2CH(OC(O)HFPO)CH2OCOCH═CH2; and

HFPO--CH2O--CH2CH(OC(O)CH═CH2)CH2OC(O)CH═CH.su-
b.2.

[0090]In other embodiments, the non-urethane fluoropolyether
poly(meth)acryl compound may be a compound preparable by Michael-type
addition of a reactive (per)fluoropolyether with a poly(meth)acrylate,
such as the adduct of HFPO--C(O)N(H)CH2CH2CH2N(H)CH3
with trimethylolpropane triacrylate (TMPTA). Such (per)fluoropolyether
acrylate compounds are further described in U.S. Pat. No. 7,342,080.

[0091]Other non-urethane fluoropolyether poly(meth)acryl compounds include
those disclosed in U.S. Pat. Nos. 3,810,874 and 4,321,404. A
representative compound is given by the structure
CH2═CHC(O)OCH2CF2O(CF2CF2O)mm(CF2O-
)nnCH2OC(O)CH═CH2, where mm and nn designate that the
number of randomly distributed perfluoroethyleneoxy and
perfluoromethyleneoxy backbone repeating units, respectively, mm and nn
having independently values, for example from 1 to 50, and the ratio of
mm/nn is 0.2 to 1 to 5/1.

[0092]Still other non-urethane fluoropolyether compounds include thiols
such as HFPO--C(O)NHCH2CH2OC(O)CH2SH and vinyl compounds
such as HFPO--C(O)NHCH2CH═CH2, and
HFPO--C(O)NHCH2CH2OCH═CH2.

[0093]In one synergistic combination, a perfluoropolyether urethane having
a perfluoropolyether moiety and a multi-(meth)acryl terminal group is
employed in combination with a (non-urethane) monofunctional
perfluoropolyether compound having a perfluoropolyether moiety linked to
a (meth)acryl group. Typically, the perfluoropolyether moiety is a
terminal group of the compound. Likewise, the (meth)acryl group is also
typically a terminal group. In another embodiment, the second
(non-urethane) perfluoropolyether compound typically has a higher weight
percent fluorine than the perfluoropolyether urethane multi-(meth)acryl
compound. It is surmised that the monofunctional perfluoropolyether
compound is the major contributor to the high contact angles; whereas the
perfluoropolyether urethane multi-(meth)acryl compound compatibilizes the
monofunctional perfluoropolyether compound. This interaction allows
higher concentration of monofunctional perfluoropolyether compound to be
incorporated without phase separation. In yet another embodiment, a
perfluoropolyether urethane having a perfluoropolyether moiety and a
multi-(meth)acryl terminal group is employed in combination with a
(non-urethane) multi-functional perfluoropolyether compound having a
perfluoropolyether moiety linked to at least two (meth)acryl group.
Alternatively, a perfluoropolyether urethane monoacrylate can be employed
in combination with a (non-urethane) mono- or multi-(meth)acryl
perfluoropolyether compound.

[0094]The fluorocarbon- and urethane (meth)acryl additives (e.g. such as
those of Formulas (1), (3A), (4), (5) or (6)), optionally in combination
with various other (per)fluoropolyether (meth)acryl compounds, may also
be combined with one or more other (non-urethane) fluorinated compounds
to improve the compatibility of the mixture.

[0095]A class of free-radically reactive fluoroalkyl or fluoroalkylene
group-containing compatibilizers includes compounds of the respective
chemical formulas: RffQ3(X1)n1 and
(X1)n1Q3Rff2Q3(X1)n1), where Rif
is a fluoroalkyl, Rf is a fluoroalkylene, Q3 is a connecting
group of valency at least 2 and is selected from the group consisting of
a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene
group, a straight or branched chain or cycle-containing connecting group
optionally containing heteroatoms such as O, N, and S and optionally a
heteroatom-containing functional group such as carbonyl or sulfonyl, and
combinations thereof; X1 is a free-radically reactive group selected
from (meth)acryl, --SH, allyl, or vinyl groups and n1 is independently 1
to 3. Typical Q3 groups include: --SO2N(R)CH2CH2--;
--SO2N(CH2CH2)2--; --(CH2)m--;
--CH2O(CH2)3--; and --C(O)NRCH2CH2--, where R is
H or lower alkyl of 1 to 4 carbon atoms and m is 1 to 6. Preferably the
fluoroalkyl or fluoroalkylene group is a perfluoroalkyl or
perfluoroalkylene group. One preferred class of fluoroalkyl- or
alkylene-substituted compatibilizers meeting these criteria for use in
the composition of the hard coat layer 18 is the
perfluorobutyl-substituted acrylate compatibilizers. Exemplary,
non-limiting perfluorobutyl-substituted acrylate compatibilizers meeting
these criteria and useful in the present invention include one or more of
C4F9SO2N(CH3)CH2CH2OC(O)CH═CH2,
C4F9SO2N(CH2CH2OC(O)CH═CH2)2, or
C4F9SO2N(CH3)CH2CH2OC(O)C(CH3)═CH.-
sub.2.

[0096]The free-radically reactive fluoroalkyl or fluoroalkylene
group-containing compatibilizers described above are preferably added at
between about 0.5% and 20%, and more preferably between about 1% and 10%,
of the total solids of the hard coat composition. One non-limiting
example of a preferred fluoroalkyl-substituted compatibilizer that may be
utilized in the composition of the hard coat layer 18 is: (1H, 1H, 2H,
2H)-perfluorodecyl acrylate, available from Lancaster Synthesis of
Windham, N.H. Numerous other (meth)acryl compounds with perfluoroalkyl
moieties that may also be utilized in the composition of the hard coat
layer are mentioned in U.S. Pat. No. 4,968,116, to Hulme-Lowe et al., and
in U.S. Pat. No. 5,239,026 (including perfluorocyclohexylmethyl
methacrylate), to Babirad et al., which are herein incorporated by
reference. Other fluorochemical (meth)acrylates that meet these criteria
and may be utilized include, for example,
2,2,3,3,4,4,5,5-octafluorohexanediol diacrylate and ω-hydro
2,2,3,3,4,4,5,5-octafluoropentyl acrylate
(H--C4F8--CH2O--C(O)--CH═CH2). Other
fluorochemical (meth)acrylates that may be used alone, or as mixtures,
are described in U.S. Pat. No. 6,238,798, to Kang et al., and herein
incorporated by reference.

[0097]Another compatibilizer that may be used is a fluoroalkyl- or
fluoroalkylene-substituted thiol or polythiol. Non-limiting examples of
this type of compatibilizer includes one or more of the following:
C4F9SO2N(CH3)CH2CH2OC(O)CH2SH,
C4F9SO2N(CH3)CH2CH2OC(O)CH2CH2SH,
C4F9SO2N(CH3)CH2CH2SH, and
C4F9SO2N(CH3)CH(OC(O)CH2SH)CH2OC(O)CH2-
SH.

[0098]In some embodiments, as little as 1 wt-% of the non-urethane
fluorinated compound will phase separate from a hydrocarbon
multifunctional acrylate such as trimethyol propane triacrylate. Such
phase separation is undesirable in the hardcoats of this invention since
it can lead to optically nonuniform coatings. In these embodiments, the
fluorocarbon- and urethane-(meth) acryl compositions(s) can be added to
the curable mixture such that the weight ratio of the fluorocarbon
urethane additive to non-urethane perfluoropolyether, fluoroalkyl, or
fluororalkylene (meth)acryl compound is 1:1, preferably 2:1 and most
preferably 3:1. Within these preferred ratios the total weight percent
fluorine of the curable mixture may comprise from 0.5-25 wt-% fluorine,
preferably 0.5 to 10 wt-% fluorine, and most preferably 0.5 to 5-wt %
flourine, without the non-urethane fluorinated (meth)acryl compound phase
separating from the mixture. The non-urethane containing
perfluoropolyether can have molecular weights of greater than 300 g/mol
to 3000 g/mol, contain mono (meth)acryl functionality, or
multi-(meth)acryl functionality. The (meth)acryl functionality can be
located at one or both termini or as a branch point in the molecule.

[0099]The hardcoat may be provided as a single layer disposed on an
optical substrate. In this construction, the total of all
(per)fluorinated compounds, (e.g. the perfluoropolyether urethane(s)
alone or in combination with other fluorinated compounds) ranges from
0.01% to 10%, and more preferably from 0.1% to 1%, of the total solids of
the hard coat composition. For embodiments wherein a (e.g. inorganic
particle-containing) hardcoat layer is disposed between the optical
substrate and hardcoat surface layer, the amount of perfluoropolyether
urethane(s) in the coating compositions ranges from 0.01 to 50 wt-%
solids, and more preferably from 1 to 25 wt-% solids; whereas the various
other (per)fluoropolyether acryl compounds may be present at weight
percents from 1 to 20%, and preferably from 1 to 10%. Preferably, the
ratio of fluorocarbon- and urethane-(meth)acryl-containing additive to
other non-urethane fluorinated compounds is at least 1 to 1 and more
preferably is about 3 to 1.

[0100]The conventional hard coat material used as a portion of layer 18 in
any of the preferred embodiments described above is a hydrocarbon-based
material well known to those of ordinary skill in the optical arts. Most
preferably, the hydrocarbon-based material is an acrylate-based hard coat
material. One preferable hard coat material for use in the present
invention is based on PETA (pentaerythritol tri/tetra acrylate). One
commercially available form of pentaerythritol triacrylate ("PET3A") is
SR444c and one commercially available form of pentaerythritol
tetraacrylate ("PET4A") is SR295, each available from Sartomer Company of
Exton, Pa.

[0102]It is typically preferred to maximize the concentration of
crosslinker particularly since non-fluorinated (meth)acrylate
crosslinkers are generally less expensive than fluorinated compounds.
Accordingly, the coating compositions described herein typically comprise
at least 20 wt-% crosslinking agent(s). The total amount of crosslinking
agent(s) may comprise at least 50 wt-% and may be for example at least 60
wt-%, at least 70 wt-%, at least 80 wt-%, at least 90 wt-% and even about
95 wt-% of the coating composition.

[0103]To facilitate curing, polymerizable compositions according to the
present invention may further comprise at least one free-radical thermal
initiator and/or photoinitiator. Typically, if such an initiator and/or
photoinitiator are present, it comprises less than about 10 percent by
weight, more typically less than about 5 percent of the polymerizable
composition, based on the total weight of the polymerizable composition.
Free-radical curing techniques are well known in the art and include, for
example, thermal curing methods as well as radiation curing methods such
as electron beam or ultraviolet radiation. Further details concerning
free radical thermal and photopolymerization techniques may be found in,
for example, U.S. Pat. Nos. 4,654,233 (Grant et al.); 4,855,184 (Klun et
al.); and 6,224,949 (Wright et al.).

[0105]Useful free-radical photoinitiators include, for example, those
known as useful in the UV cure of acrylate polymers. Such initiators
include benzophenone and its derivatives; benzoin, alpha-methylbenzoin,
alpha-phenylbenzoin, alpha-allylbenzoin, alpha-benzylbenzoin; benzoin
ethers such as benzil dimethyl ketal (commercially available under the
trade designation "IRGACURE 651" from Ciba Specialty Chemicals
Corporation of Tarrytown, N.Y.), benzoin methyl ether, benzoin ethyl
ether, benzoin n-butyl ether; acetophenone and its derivatives such as
2-hydroxy-2-methyl-1-phenyl-1-propanone (commercially available under the
trade designation "DAROCUR 1173" from Ciba Specialty Chemicals
Corporation) and 1-hydroxycyclohexyl phenyl ketone (commercially
available under the trade designation "IRGACURE 184", also from Ciba
Specialty Chemicals Corporation);
2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone
commercially available under the trade designation "IRGACURE 907", also
from Ciba Specialty Chemicals Corporation);
2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone
commercially available under the trade designation "IRGACURE 369" from
Ciba Specialty Chemicals Corporation); aromatic ketones such as
benzophenone and its derivatives and anthraquinone and its derivatives;
onium salts such as diazonium salts, iodonium salts, sulfonium salts;
titanium complexes such as, for example, that which is commercially
available under the trade designation "CGI 784 DC", also from Ciba
Specialty Chemicals Corporation); halomethylnitrobenzenes; and mono- and
bis-acylphosphines such as those available from Ciba Specialty Chemicals
Corporation under the trade designations "IRGACURE 1700", "IRGACURE
1800", "IRGACURE 1850","IRGACURE 819" "IRGACURE 2005", "IRGACURE 2010",
"IRGACURE 2020" and "DAROCUR 4265". Combinations of two or more
photoinitiators may be used. Further, sensitizers such as 2-isopropyl
thioxanthone, commercially available from First Chemical Corporation,
Pascagoula, Miss., may be used in conjunction with photoinitiator(s) such
as "IRGACURE 369".

[0106]The composition of any of these embodiments is applied to an optical
substrate layer or light transmissible substrate and photocured to form
the easy to clean, stain and ink repellent light transmissible surface
layer. The presence of the urethane functionality, in addition to the
fluorocarbon component, in the additive can eliminate the need for
comonomers introduced to the composition to compatibilize the
fluorochemical component with the hydrocarbon-based crosslinker.

[0108]A variety of inorganic oxide particles can be used in the hardcoat.
The particles are typically substantially spherical in shape and
relatively uniform in size. The particles can have a substantially
monodisperse size distribution or a polymodal distribution obtained by
blending two or more substantially monodisperse distributions. The
inorganic oxide particles are typically non-aggregated (substantially
discrete), as aggregation can result in precipitation of the inorganic
oxide particles or gelation of the hardcoat. The inorganic oxide
particles are typically colloidal in size, having an average particle
diameter of about 0.001 to about 0.2 micrometers, less than about 0.05
micrometers, and less than about 0.03 micrometers. These size ranges
facilitate dispersion of the inorganic oxide particles into the binder
resin and provide ceramers with desirable surface properties and optical
clarity. The average particle size of the inorganic oxide particles can
be measured using transmission electron microscopy to count the number of
inorganic oxide particles of a given diameter. The inorganic oxide
particles can consist essentially of or consist of a single oxide such as
silica, or can comprise a combination of oxides, such as silica and
aluminum oxide, or a core of an oxide of one type (or a core of a
material other than a metal oxide) on which is deposited an oxide of
another type. Silica is a common inorganic particle. The inorganic oxide
particles are often provided in the form of a sol containing a colloidal
dispersion of inorganic oxide particles in liquid media. The sol can be
prepared using a variety of techniques and in a variety of forms
including hydrosols (where water serves as the liquid medium), organosols
(where organic liquids so serve), and mixed sols (where the liquid medium
contains both water and an organic liquid), e.g., as described in U.S.
Pat. Nos. 5,648,407 (Goetz et al.); 5,677,050 (Bilkadi et al.) and
6,299,799 (Craig et al.), the disclosure of which is incorporated by
reference herein. Aqueous sols (e.g. of amorphous silica) can be
employed. Sols generally contain at least 2 wt-%, at least 10 wt-%, at
least 15 wt-%, at least 25 wt-%, and often at least 35 wt-% colloidal
inorganic oxide particles based on the total weight of the sol. The
amount of colloidal inorganic oxide particle is typically no more than 50
wt-% (e.g. 45 wt-%). The surface of the inorganic particles can be
"acrylate functionalized" as described in Bilkadi et al. The sols can
also be matched to the pH of the binder, and can contain counterions or
water-soluble compounds (e.g., sodium aluminate), all as described in
Kang et al. '798.

[0109]One example of such particles is colloidal silica reacted with a
methacryl silane coupling agent such as A-174 (available from Natrochem,
Inc.), other dispersant aids such as N,N dimethylacrylamide and various
other additives (stabilizers, initiators, etc.).

[0110]A particulate matting agent can be incorporated into the
polymerizable composition in order to impart anti-glare properties to the
surface layer. The particulate matting agent also prevents the
reflectance decrease and uneven coloration caused by interference with an
associated hard coat layer. The particulate matting agent should
preferably be transparent, exhibiting transmission values of greater than
about 90%. Alternatively, or in addition thereto, the haze value is
preferably less than about 5%, and more preferably less than about 2%,
and most preferably less than about 1%.

[0111]Exemplary systems incorporating matting agents into a hard coating
layer, but having a different hard coating composition, are described,
for example, in U.S. Pat. No. 6,693,746, and herein incorporated by
reference. Further, exemplary matte films are commercially available from
U.S.A. Kimoto Tech of Cedartown, Ga., under the trade designation
"N4D2A."

[0112]The amount of particulate matting agent added is between about 0.5
and 10% of the total solids of the composition, depending upon the
thickness of the layer 18, with a preferred amount around 2%. The
anti-glare layer 18 preferably has a thickness of 0.5 to 10 microns, more
preferably 0.8 to 7 microns, which is generally in the same thickness
range of gloss hard coatings.

[0113]The average particle diameter of the particulate matting agent has a
predefined minimum and maximum that is partially dependent upon the
thickness of the layer. However, generally speaking, average particle
diameters below 1.0 microns do not provide the degree of anti-glare
sufficient to warrant inclusion, while average particle diameters
exceeding 10.0 microns deteriorate the sharpness of the transmission
image. The average particle size is thus preferably between about 1.0 and
10.0 microns, and more preferably between 1.7 and 3.5 microns, in terms
of the number-averaged value measured by the Coulter method.

[0114]As the particulate matting agent, inorganic particles or resin
particles are used including, for example, amorphous silica particles,
TiO2 particles, Al2O3 particles, cross-linked acrylic
polymer particles such as those made of cross-linked poly(methyl
methacrylate), cross-linked polystyrene particles, melamine resin
particles, benzoguanamine resin particles, and cross-linked polysiloxane
particles. By taking into account the dispersion stability and
sedimentation stability of the particles in the coating mixture for the
anti-glare layer and/or the hard coat layer during the manufacturing
process, resin particles are more preferred, and in particular
cross-linked polystyrene particles are preferably used since resin
particles have a high affinity for the binder material and a small
specific gravity.

[0115]As for the shape of the particulate matting agent, spherical and
amorphous particles can be used. However, to obtain a consistent
anti-glare property, spherical particles are desirable. Two or more kinds
of particulate materials may also be used in combination.

[0116]Other types of inorganic particles can be incorporated into the hard
coats of this invention. Particularly preferred are conducting metal
oxide nanoparticles such as antimony tin oxide, fluorinated tin oxide,
vanadium oxide, zinc oxide, antimony zinc oxide, and indium tin oxide.
They can also be surface treated with materials such as
3-methacryloxypropyltrimethoxysilane. These particles can provide
constructions with antistatic properties. This is desirable to prevent
static charging and resulting contamination by adhesion of dust and other
unwanted debris during handling and cleaning of the film. Preferably,
such metal oxide particles are incorporated into the top (thin) layer of
the two-layer constructions of this invention, in which the fluorinated
hardcoat is applied to a hydrocarbon-based hardcoat. At the levels at
which such particles may be needed in the coating in order to confer
adequate antistatic properties (typically 25 wt % and greater), these
deeply colored particles can impart undesired color to the construction.
However, in the thin top layer of a two-layer fluorinated hardcoat
construction, their effect on the optical and transmission properties of
the film is minimized. Examples of conducting metal oxide nanoparticles
useful in this embodiment include antimony double oxide available from
Nissan Chemical under the trade designations Celnax CXZ-2101P and
CXZ-2101P-F2. When these particles are included at appropriate levels in
the coatings of this invention, the resulting fluorinated hardcoats can
exhibit static charge decay times less than about 0.5 sec. In this test,
the sample is placed between two electrical contacts and charged to +/-5
kV. The sample is then grounded, and the time necessary for the charge to
decay to 10% of its initial value is measured and recorded as the static
charge decay time. In contrast, film constructions containing no
conducting nanoparticles exhibit static charge decay times >30 sec.

[0118]A die coater generally refers to an apparatus that utilizes a first
die block and a second die block to form a manifold cavity and a die
slot. The coating fluid, under pressure, flows through the manifold
cavity and out the coating slot to form a ribbon of coating material.
Coatings can be applied as a single layer or as two or more superimposed
layers. Although it is usually convenient for the substrate to be in the
form of a continuous web, the substrate may also be a succession of
discrete sheets.

[0119]To prove the effectiveness of the hard coat formulations according
to each preferred embodiment of the present invention described above,
sample hard coats having the given compositions were formulated and
applied to PET substrates and compared to hard coat formulations having
less than all the desired components. The coatings were visually
inspected and tested for ink repellency, durability and surface
roughness. The experimental procedures and tabulated results are
described below:

I. Experimental Procedures:

A: Ingredients

[0120]Unless otherwise noted, as used in the examples, "HFPO--" refers to
the end group F(CF(CF3)CF2O)aCF(CF3)-- of the methyl
ester F(CF(CF3)CF2O)aCF(CF3)C(O)OCH3 wherein a
averages about 6.22, with an average molecular weight of 1,211 g/mol, can
be prepared according to the method reported in U.S. Pat. No. 3,250,808
(Moore et al.), the disclosure of which is incorporated herein by
reference, with purification by fractional distillation.

Polyisocyanates Desmodur® (Des) N100, Desmodur® 3300, Desmodur®
TPLS2294, Desmodur® N 3600, and Isophorone diisocyanate (IPDI) were
obtained from Bayer Polymers LLC, of Pittsburgh, Pa.PAPI (Poly[(phenyl
isocyanate)-co-formaldehyde]) (MW about 375), is available from Sigma
Aldrich of Milwaukee, Wis.C6F13C2H4OH is available
from Sigma Aldrich of Milwaukee, Wis.4-methoxy phenol (MEHQ) is available
from Sigma Aldrich of Milwaukee, Wis.HO(CH2)10OH is available
from Sigma Aldrich of Milwaukee, Wis.FOX-diol
(H(OCH2CCH3(CH2OCH2CF3)CH2)xOH) (MW
about 1342), is available from Omnova Solutions Inc. of Akron,
Ohio.Pentaerythritol tetracrylate ("PET4A"), under the trade designation
"SR295", was obtained from Sartomer Company of Exton, Pa.Pentaerythritol
triacrylate ("PET3A"), under the trade designation "SR444C", was obtained
from Sartomer Company of Exton, Pa.Trimethylolpropane triacrylate
("TMPTA"), under the trade designation "SR351", was obtained from
Sartomer Company of Exton, Pa.Hydantoin hexaacrylate (HHA) was prepared
as described in Example 1 of U.S. Pat. No. 4,262,072.FBSEE
(C4F9SO2N(C2H4OH)2), a fluorochemical diol,
can be prepared as described in column 5, line 31 and in FIG. 9 of U.S.
Pat. No. 3,734,962 (1973).MeFBSE
(C4F9SO2N(CH3)CH2CH2OH) was prepared by
essentially following the procedure described in U.S. Pat. No. 6,664,354
(Savu et al.), Example 2, Part A.FBSEA
(C4F9SO2N(CH3)CH2CH2OC(O)CH═CH2)
is made by the procedure of Examples 2A and 2B of WO 01/30873 to Savu et
al.HFPO-AEA (HFPO--C(O)NHCH2CH2OC(O)CH═CH2) was
prepared as described in File number U.S. Pat. No. 7,101,618; under
Preparation of Monofunctional Perfluoropolyether Acrylate (FC-1).
Hereafter its use is noted as 31a.Fomblin Zdol
(HOCH2CF2(OCF2CF2)(OCF2), CH2OH) is
available from Solvay Solexis, Inc. of Italy.LTM diacrylate,
CH2═CHC(O)OCH2CF2O(CF2CF2O)mm(CF2O-
)nnCH2OC(O)CH═CH2 was prepared from Fomblin Zdol
according to the procedure of Example XV of U.S. Pat. No.
3,810,874.Hydroxyethyl acrylate (HEA) is available from Sigma Aldrich of
Milwaukee, Wis.H2NCH2CH2CH2Si(OCH3)3 is
available from Sigma Aldrich of Milwaukee,
Wis.HSCH2CH2CH2Si(OCH3)3 is available from Sigma
Aldrich of Milwaukee, Wis.2-isocyanato-ethyl methacrylate ("IEM")
(CH2═C(CH3)CO2CH2CH2NCO), is available from Sigma
Aldrich of Milwaukee, Wis.CN 4000 is available from Sartomer Company of
Exton, Pa. It is an α, ω difunctional perfluoropolyether
oligomer with 55% wt fluorine and a molecular weight of approximately
2000 g/mol.The amines, triethylamine, 2-amino-2-ethyl-1,3-propanediol,
and 1,1-bis-(hydroxyethyl)-1,3 aminopropane were obtained from
Sigma-Aldrich of Milwaukee, Wis.Acryloyl chloride was obtained from
Sigma-Aldrich of Milwaukee Wis.The UV photoinitiator, 1-hydroxycyclohexyl
phenyl ketone used was obtained from Ciba Specialty Products, Tarrytown,
N.Y. and sold under the trade designation "Irgacure 184."The
photoinitiator 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one
used was obtained from Ciba Specialty Products, Tarrytown, N.Y. and sold
under the trade designation "Irgacure 907."Methyl perfluorobutyl ether
(HFE 7100) was obtained from 3M Company, St. Paul, Minn.Dibutyltin
dilaurate (DBTDL) was obtained from Sigma Aldrich of Milwaukee, Wis.

B. Preparation of Experimental Materials

[0121]Unless otherwise noted, "MW" refers to molecular weight and "EW"
refers to equivalent weight. Further, "° C." may be used
interchangeably with "degrees Celsius" and "mol" refers to moles of a
particular material and "eq" refers to equivalents of a particular
material. Further, "Me" constitutes a methyl group and may be used
interchangeably with "CH3."

Preparation No. 1. Preparation of HFPO--C(O)OCH3

[0122]As used in the examples, "HFPO--" refers to the end group
F(CF(CF3)CF2O)aCF(CF3)-- wherein a has average values
of about 4.41, 6.2, 6.85, and 8.07. The material
F(CF(CF3)CF2O)aCF(CF3)COOCH3
(HFPO--C(O)OCH3) can be prepared according to the method reported in
U.S. Pat. No. 3,250,808 (Moore et al.), the disclosure of which is
incorporated herein by reference, with purification by fractional
distillation.

[0124]To a 500 ml 3-necked flask equipped with a stir bar and reflux
condenser was charged 11.91 g (0.1 mol)
H2NC(CH2OH)2CH2CH3 and 60 g tetrahydrofuran
("THF"). Next via dropping funnel was added 121.1 g (0.1 mol)
HFPO--C(O)OCH3 over about 80 minutes at a bath temperature of about
85 degrees Celsius. The reaction was cloudy at first, but became clear
about 1 hour into the reaction. After addition was complete, the heating
bath was shut off and the reaction was allowed to cool for three days.
The material was concentrated at 55 degrees Celsius under aspirator
vacuum to yield 130.03 g of a light colored syrup. NMR analysis showed
the product to be an 87:13 mixture of the structures I and II as follows:

##STR00003##

Preparation No. 4a. Preparation of HFPO--C(O)NHCH2CH2OH

[0125]HFPO--C(O)N(H)CH2CH2OH of different molecular weights
(938.5, 1344, and 1547.2) were made by a procedure similar to that
described in U.S. Pat. No. 7,094,829, with the exception that
F(CF(CF3)CF2O)aCF(CF3)C(O)CH3 with a=6.2 was
replaced with F(CF(CF3)CF2O)aCF(CF3)C(O)OCH3
wherein a=4.41, 6.85, and 8.07 respectively.

[0126]Preparation No. 4b, Synthesis of
HFPOC(O)--NH--CH2CH2--O--CH2CH2--OCH2CH2--O-
H Starting Material (i.e. HFPO-EO3-OH)HFPO--C(O)OCH3 (Mw=1340 g/mole.
100.0 g) was placed in a 500 ml round bottom flask. The flask was purged
with nitrogen and placed in a water bath to maintain a temperature of
50° C. or less. To this flask was added 9.5 g (0.091 mol) of
2-aminoethoxyethoxyethanol (obtained from Huntsman Chemicals of Austin,
Tex. as XTA-250.) The reaction mixture was observed to be initially two
phases, but with stirring, it gradually turned light yellow and
homogenized within about 30 min. The reaction mixture was allowed to stir
for 48 hrs. After this time an infrared spectrum of the reaction mixture
showed complete loss of the methyl ester band at 1780 cm-1 and the
presence of the strong amide carbonyl stretch at 1718 cm-1. Methyl
t-butyl ether (200 ml) was added to the reaction mixture and the organic
phase was extracted twice with water/HCl (˜15%) to remove unreacted
amine and methanol. The MTBE layers were combined and dried with
MgSO4. The MTBE was removed under reduced pressure to yield a clear,
viscous liquid. Further drying at 0.1 mm Hg at room temperature for 16
hrs, resulted in 101.3 g (90% yield). 1H NMR and IR spectroscopy
confirmed the formation of the above-identified compound HFPO-EO3-OH.

[0127]The same synthetic process was used for the preparation of
HFPO-EO4-OH as the EO3-OH adduct except the starting amino-EO4-alcohol,
aminoethoxyethoxyethoxy ethanol was used instead of amino EO3. EO-4
alcohol was obtained from Huntsman Chemicals of Austin, Tex. as XTA-350

[0128]Preparation No. 4d, Synthesis of HFPOC(O)--NH--(CH2)6--OH
Starting Material (i.e. HFPO-AH-OH) The same synthetic procedure was used
for the preparation of HFPO-AH-OH as the EO3-OH adduct except the
starting aminoalcohol was 6-amino-hexanol available from Aldrich Chemical
Co. Milwaykee, Wis.

[0129]A 500 ml roundbottom flask equipped with magnetic stir bar was
charged with 25.0 g (0.131 eq, 191 EW) Des N100, 43.13 g (0.087 eq, 494.3
EW) of Sartomer SR444c, 25.3 mg of MEHQ, and 126.77 g methyl ethyl ketone
(MEK). The reaction was swirled to dissolve all the reactants, the flask
was placed in a oil bath at 60 degrees Celsius, and fitted with a
condenser under dry air. Two drops of dibutyltin dilaurate was added to
the reaction. After 1 hour, 58.64 g (0.0436 eq, 1344 EW)
F(CF(CF3)CF2O)6.85CF(CF3)C(O)NHCH2CH2OH was
added to the reaction via addition funnel over about 75 minutes. The
reaction was monitored by FTIR and showed a small isocyanate absorption
at 2273 cm-1 after about 5 hours of reaction, but no isocyanate
absorption at 7.5 hours of reaction. The material was used as a 50%
solids solution in MEK. The HFPO multiacrylate urethanes preparations
shown in Table 1 below, listed as Preparation Nos. 5.1 through 5.19
respectively, were all made according to this general procedure, using
the appropriate mole fractions of materials noted in the table.

[0130]A 500 ml roundbottom 2-necked flask equipped with magnetic stir bar
was charged with 25.00 g (0.131 eq, 191 EW) Des N100, 26.39 g (0.0196 eq,
1344 EW) F(CF(CF3)CF2O)6.85
CF(CF3)C(O)NHCH2CH2OH, and 109.62 g MEK, and was swirled
to produce a homogeneous solution. The flask was placed in an 80 degrees
Celsius bath, charged with 2 drops of dibutyltin dilaurate catalyst, and
fitted with a condenser. The reaction was cloudy at first, but cleared
within two minutes. At about 1.75 hours, the flask was removed from the
bath and 2.42 g of MEK was added to compensate for lost solvent. A 2.0 g
sample was removed from the flask, leaving (1-(2.0/161.01) or 0.9876
weight fraction, of the reaction, and 57.51 g (98.76% of 58.23 g) (0.116
mol, 494.3 equivalent weight) PET3A was added to the reaction, which was
placed in a 63 degrees Celsius bath. At about 5.25 hours FTIR showed no
isocyanate absorption at 2273 cm-1, and 0.56 g MEK was added to
compensate for solvent lost to bring the material to 50% solids. The
product has a calculated wt % F of 15.6% F)

[0146]The preparation of other perfluoropolyether urethane multiacrylates
containing trialkoxysilane functionality was done by a similar procedure,
substituting the appropriate amounts of materials, and are summarized in
Table 2 as Preparation Nos. 20.1 through 20.4:

[0148]A 1-liter round-bottom flask was charged with 291.24 g (0.2405 mol)
of HFPO--C(O)OCH3 and 21.2 g (0.2405 mol)
N-methyl-1,3-propanediamine, both at room temperature, resulting in a
cloudy solution. The flask was swirled and the temperature of the mixture
rose to 45 degrees Celsius, and to give a water-white liquid, which was
heated overnight at 55 degrees Celsius. The product was then placed on a
rotary evaporator at 75 degrees Celsius and 28 inches of Hg vacuum to
remove methanol, yielding 301.88 g of a viscous slightly yellow liquid,
nominal molecular weight is equal to 1267.15 g/mol.

[0151]The title material was prepared as described in U.S. Patent
Application Publication No. 2005/0249940, referred to as FC-4 and had a
calculated wt-% fluorine of 58.5%

[0152]Preparation No. 26. Preparation of
CH3(O)CCF(CF3)(OCF2CF(CF3)bOCF2CF2CF.s-
ub.2CF2O(CF(CF3)CF2O)cCF(CF3)COOCH3
(H3CO(O)C--HFPO--C(O)OCH3)H3CO(O)C--HFPO--C(O)OCH3,
in which b+c average about 4.5 can be prepared using
FC(O)CF2CF2C(O)F as an initiator according to the method
reported in U.S. Pat. No. 3,250,807 (Fritz, et al.) which provides the
HFPO oligomer bis-acid fluoride, followed by methanolysis and
purification by removal of lower boiling materials by fractional
distillation as described in U.S. Pat. No. 6,923,921 (Flynn, et. al.).
The disclosure of both aforementioned patents are incorporated herein by
reference.

[0153]A 200 ml roundbottom flask equipped with magnetic stirbar was
charged with 3.81 g (0.0624 mol) ethanolamine and heated to 75 degrees
Celcius under a dry air. A charge of 30.0 g (0.240 mol, 1250 MW)
H3CO(O)C--HFPO--C(O)OCH3 was added via a pressure equalizing
funnel over 40 min and the reaction was allowed to heat for about 18 h.
From Fourier Transform Infrared Spectroscopy (FTIR) analysis, the amide
--C(O)NH-- was formed as the ester signal (--CO2--) disappeared.
Next 50.7 g of methyl t-butyl ether was added to the reaction to provide
a solution that was washed successively with 20 ml of 2N aqueous HCl, and
then 3 times with 20 ml of water. The solution was then dried over
anhydrous magnesium sulfate, filtered and concentrated on a rotary
evaporator at aspirator pressure in a 75 degrees Celcius water bath to
provide the product as a thick syrup.

[0154]A 500 ml roundbottom equipped with stirbar was charged with 40.00 g
(0.0306 mol, 1308.6 MW)
HOCH2CH2N(H)(O)C--HFPO--C(O)N(H)CH2CH2OH, 6.64 g
(0.0734 mol) triethylamine, and 54.36 g MTBE and heated at 40 degrees
Celcius. A charge of 6.64 g (0.734 mol) of acryloyl chloride was added
via pressure equalizing funnel over about 30 min, and the reaction was
allowed to heat for about 18 h. The reaction was washed with 40 g 1N HCl,
with addition of 60 g of brine and 60 g of MTBE, followed by a wash with
50 g of 5% aqueous sodium carbonate and 50 g of brine, and was finally
dried over anhydrous magnesium sulfate, filtered and concentrated on a
rotary evaporator at aspirator pressure in a 75 degrees Celcius water
bath to provide the product as a thick syrup. It has a calculated wt-%
fluorine of 58.1%.

[0155]In a manner similar to the preparation of 27, 65.00 g (0.520 mol)
H3CO(O)C--HFPO--C(O)OCH3, was reacted with 16.11 g (0.1352 mol)
2-amino-2-ethyl-1,3-propanediol to provide after the desired product as a
thick slightly yellow syrup.

[0157]Preparation 31a. HFPO AEA
(HFPO--C(O)NHCH2CH2OC(O)CH═CH2) was prepared as
described in U.S. Pat. No. 7,101,618; under Preparation of Monofunctional
Perfluoropolyether Acrylate (FC-1). It has a calculated wt % F of 62.5%

[0158]Preparation 31b, Synthesis of HFPO-EO3-A; was prepared in a manner
similar to 31aHFP0 AEA except the HFPO-amidol, 4b (HFPO-EO3-OH) was used
in place of 4a. It has a calculated wt % F of 59.1%

[0159]Preparation 31c, Synthesis of HFPO-EO4-A; was prepared in a manner
similar to HFPO-AEA 31a except the HFPO-amidol, 4c (HFPO-EO4-OH) was used
in place of 4a. It has a calculated wt % F of 57.4%

[0160]Preparation 31d, Synthesis of HFPO-AH-A; was prepared in a manner
similar to HFPO-- AEA 31a except the HFPO-amidol, 4d (HFPO-AH-OH) was
used in place of 4a. It has a calculated wt % F of 60.4%

E. Test Methods

[0161]Steel Wool Testing: The abrasion resistance of the cured films was
tested cross-web to the coating direction by use of a mechanical device
capable of oscillating cheesecloth or steel wool fastened to a stylus (by
means of a rubber gasket) across the film's surface. The stylus
oscillated over a 10 cm wide sweep width at a rate of 3.5 wipes/second
wherein a "wipe" is defined as a single travel of 10 cm. The stylus had a
flat, cylindrical geometry with a diameter of 1.25 inch (3.2 cm). The
device was equipped with a platform on which weights were placed to
increase the force exerted by the stylus normal to the film's surface.
The cheesecloth was obtained from Summers Optical, EMS Packaging, a
subdivision of EMS Acquisition Corp., Hatsfield, Pa. under the trade
designation "Mil Spec CCC-c-440 Product # S12905". The cheesecloth was
folded into 12 layers. The steel wool was obtained from Rhodes-American,
a division of Homax Products, Bellingham, Wash. under the trade
designation "#0000-Super-Fine" and was used as received. A single sample
was tested for each example, with the weight in grams applied to the
stylus and the number of wipes employed during testing reported.

[0162]Taber Testing: The Taber test was run according to ASTM D1044-99
using CS-10 wheels.

[0163]Contact Angle: The coatings were rinsed for 1 minute by hand
agitation in IPA before being subjected to measurement of water and
hexadecane contact angles. Measurements were made using as-received
reagent-grade hexadecane (Aldrich) and deionized water filtered through a
filtration system obtained from Millipore Corporation (Billerica, Mass.),
on a video contact angle analyzer available as product number VCA-2500XE
from AST Products (Billerica, Mass.). Reported values are the averages of
measurements on at least three drops measured on the right and the left
sides of the drops. Drop volumes were 5 μL for static measurements and
1-3 μL for advancing and receding. For hexadecane, only advancing and
receding contact angles are reported because static and advancing values
were found to be nearly equal.

[0164]Surface Smoothness (Dewetting): For some of the tables below, a
visual inspection was made regarding the smoothness of the applied dry
film. While the measurement of smoothness by visual inspection is a
subjective determination, a smooth film, for the purposes of the present
invention, is deemed to be a surface layer that is substantially
continuous and free of visible defects in reflected light as observed by
visual observation of the coating surface at a wide variety of possible
angles. Typically, visual observation is accomplished by looking at the
reflection of a light source from the coating surface at an angle of
about 60 degrees from perpendicular. Visual defects that may be observed
include but are not limited to pock marks, fish eyes, mottle, lumps or
substantial waviness, or other visual indicators known to one of ordinary
skill in the art in the optics and coating fields. Thus, a "rough"
surface as described below has one or more of these characteristics, and
may be indicative of a coating material in which one or more components
of the composition are incompatible with each other. Conversely, a
substantially smooth coating, characterized below as "smooth" for the
purpose of the present invention, presumes to have a coating composition
in which the various components, in the reacted final state, form a
coating in which the components are compatible or have been modified to
be compatible with one another and further has little, if any, of the
characteristics of a "rough" surface.

[0165]The surfaces may also be classified for dewetting as "good," "very
slight" (v.sl), "slight" (sl), "fair," or "poor." A "good" surface
meaning a substantially smooth surface having little dewetting. A "very
slight," slight", or "fair" categorization means that the surface has an
increasing portion of defects but is still substantially acceptable for
smoothness. A "poor" surface has a substantial amount of defects,
indicating a rough surface that has a substantial amount of dewetting.

[0166]Durability of Ink Repellency was assessed using a modified
Oscillating Sand Method (ASTM F 735-94). An orbital shaker was used (VWR
DS-500E, from VWR Bristol, Conn.). A disk of diameter 89 mm was cut from
the sample, placed in a 16 ounce jar lid (jar W216922 from Wheaton,
Millville, N.J.), and covered with 50 grams of 20-30 mesh Ottawa sand
(VWR, Bristol, Conn.). The jar was capped and placed in the shaker set at
300 rpm for 15 minutes. After shaking, a Sharpie permanent marker was
used to draw a line across the diameter of the disk surface. The portion
of the ink line that did not bead up was measured. A measure of 89 mm is
equal to 100% ink repellency loss; a measure of 0 mm would be perfect
durability or 100% ink repellency (IR) loss.

F. Experiments

[0167]The ceramer hardcoat ("HC-1") used in the examples was made as
described in column 10, line 25-39 and Example 1 of U.S. Pat. No.
5,677,050 to Bilkadi, et al.

Experiment 1

[0168]Solutions as generally described in Tables 3-5 below were prepared
at 30% solids in a solvent blend of 1:1 isopropanol:ethyl acetate and
coated at a dry thickness of about 4 microns using a number 9 wire wound
rod onto 5-mil Melinex 618 film. The coatings were dried in an 80 degree
Celsius oven for 1 minute and then placed on a conveyer belt coupled to a
ultraviolet ("UV") light curing device and UV cured under nitrogen using
a Fusion 500 watt H bulb at 20 ft/min. The values reported in the Tables
refer to the percent solids of each component of the dried coating. The
coatings were then visually inspected for surface smoothness (dewetting).
The coatings were also tested for durability of ink repellency. Results
are shown in Tables 3 and 4.

[0171]Table 6 shows the results of another set of examples that was run at
two levels of additives in an HC-1 hardcoat in which the sand test was
run for 25 minutes at 300 rpm. The examples were run according to the
same procedure as examples in Table 1 described above.

[0172]Table 7 shows the results of another set of examples that was run at
two levels of additives in an HC-1 hardcoat in which the sand test was
run for 25 minutes at 300 rpm and in a separate set for 35 minutes at 300
rpm. The examples were run according to the same procedure as examples in
Table 1 described above.

[0174]Another set illustrating the use of a multi acrylate diol in the
invention, and a thiol functional trialkoxysilane was run according to
the same procedure as examples in Table 1. These results are shown in
Table 9.

[0175]An example set illustrating the trialkoxysilane functional
perfluoropolyether urethane multiacrylates, a perfluoropolyether urethane
acrylate made using hydroxyethyl acrylate, and a perfluoropolyether diol
functionalized with isocyanatoethyl methacrylate was run according to the
same procedure as examples in Table 1. These results are shown in Table
10.

[0176]A 30% solids (in a solvent blend of 1:1 isopropanol:ethyl acetate)
sample of 99.4% PET4A/0.6% Des N100/0.85 PET3A/0.15 HFPO (Preparation
5.2) with 2% added Irgacure 907 was prepared. The solution was coated and
cured by the same procedure as above. The smooth coating gave an ink
repellency of 0 after a 20 minute sand test at 300 rpm.

[0177]Another set of examples using a perfluoropolyether alcohol
functionalized with isocyanatoethyl methacrylate in combination with a
compatibilizer was run according to the same procedure as examples in
Table 1. The results are shown in Table 11.

[0178]Another experiment was run in which HC-1 was applied to the 5-mil
Melinex 618 film with a metered, precision die coating process. The
hardcoat formulation with HC-1 and Des N100/0.85 PET3A/0.15 HFPO
(Preparation 5.2) was diluted to 30 wt-% solids in isopropanol and coated
onto the 5-mil PET backing to achieve a dry thickness of 5 microns. A
flow meter was used to monitor and set the flow rate of the material from
a pressurized container. The flow rate was adjusted by changing the air
pressure inside the sealed container which forces liquid out through a
tube, through a filter, the flow meter and then through the die. The
dried and cured film was wound on a take up roll.

[0179]The coatings were dried in a 10-foot oven at 100 degrees Celsius,
and cured with a 300-watt Fusion Systems H bulb at 100, 75, 50, and 25%
power. The coating shown in Table 12 below was evaluated in a series of
tests. The sand test was run for 15 minutes at 300 rpm. The Steel Wool
Test was run checking for damage to the coating at 100, 250, 500, 750,
and 1000 cycles. The results are summarized in Table 12. Contact angles
were also run on selected samples before and after testing and these
results are shown in Table 13.

[0180]Selected coatings from Table 12 were tested for contact angles with
water and hexadecane, and are identified by the UV dose % power used in
curing the coatings. The results are summarized in Table 13:

[0181]A primed 5 mil transparent polyethylene terephthalate (PET) film was
obtained from i.i. duPont de Nemours and Company, Wilmington, Del. under
the trade designation "Melinex 618". A hardcoat composition substantially
the same as Example 3 of U.S. Pat. No. 6,299,799 (HC-1) was coated onto
the primed surface with a metered, precision die coating process. The
hardcoat was diluted in IPA to 30 wt-% solids and coated onto the 5-mil
PET backing to achieve a dry thickness of 5 microns. A flow meter was
used to monitor and set the flow rate of the material from a pressurized
container. The flow rate was adjusted by changing the air pressure inside
the sealed container which forces liquid out through a tube, through a
filter, the flow meter and then through the die. The dried and cured film
was wound on a take up roll and used as the input backing Hardcoat
Substrate S-1 for the coating solutions described below.

[0184]The coating compositions described in Table 14 were coated onto the
hardcoat layer Si using a precision, metered die coater. For this step, a
syringe pump was used to meter the solution into the die. The solutions
were diluted with MEK to a concentration of 1% and coated onto the
hardcoat layer to achieve a dry thickness of 60 nm. The material was
dried in a conventional air flotation oven and then cured a 600 watt
Fusion Systems bulb under nitrogen using the conditions show below:

[0187]MEK solutions of the mixtures shown in Table 15 were prepared at 30%
solids. After thoroughly mixing the desired components at the ratios
shown, approximately 3 ml of each soln was deposited onto a glass
microscope slide and the solvent was allowed to evaporate over 16 hrs.
The compatibility of the mixtures were than noted as either incompatible
or compatible. An "Incompatible" observation was noted when the dried,
uncured 100% solids mixture was either hazy or showed clear phase
separations such as "oil-water type" phase separation behavior.
Compatible mixtures were observed to be clear or transparent with no
visible detection of a second phase in the mixture. The mixtures were
further diluted to 1.25% solids with MEK and 4% Darocure 1173
photoinitiator based on the solid content of the solution was added to
the mixtures. An approximate 40 nm coating of each of these solutions was
prepared on the substrate S1 by the use of a #2.5 Meyer Rod. The coatings
were allowed to dry at room temperature and were cured at 10 fpm,
2-passes by use of Fusion Systems UV processor Model LCS BQ, The UV
system was equipped with a Fusion Systems 500 w Light-Hammer model LH6 PS
and used a H Bulb as the UV source. The cure chamber was flushed
continuously with a positive nitrogen flow of approximately 20 psi.
Contact angles were measured as described elsewhere in this application.

[0188]MEK solutions of the mixtures shown in Table 16 were prepared at 30%
solids. After mixing the desired components thoroughly, approximately 3
ml of each soln was deposited onto a glass microscope slide and the
solvent was allowed to evaporate. After 16 hrs, the compatibility of the
mixtures was noted according to the criteria described for Table 15.

[0190]Formulations described in Table 16, were coated on S-1 at
approximately 40 nm coating weight using the same method as described in
Table 15. Contact angle measurements and durability were determined as
previously described. The results are shown in Table 17.

[0191]Coating formulations comprising the multifunctional PFPE acrylates
(Preps 25, 28, 29), LTM diacrylate, and CN4000, were prepared at constant
weight percent fluorine by mixing with TMPTA. These compositions were
compared to Coating Formulation #9 of Table 15, to exemplify the utility
of the HFPO-U acrylate as a compatibilizer for either PFPE
Multifunctional acrylate or HFPO-monoacrylates. The compositions are
shown in Table 18 and the surface contact angles and durabilities are
shown in Table 19.

[0192]While the invention has been described in terms of preferred
embodiments, it will be understood, of course, that the invention is not
limited thereto since modifications may be made by those skilled in the
art, particularly in light of the foregoing teachings.